Dis and poly azodyestuffs



Patented Jan. 6, 1931" UNITED smres masses PATENT lorries wmrarn HEN-THIGH AND Max HARDTMANN, or winsDoaaoN-rnn-Rmnn, 'RUnoLr Kansas, or LEVERKUSEN-ON-THE-RHINE,' AND, JOSEF HILGER, or COLOGNE-MUL- HErM, GERMANY, nssrenoss T0 QENERAL ANILINE woaKs, me, or new YORK,

N. Y., A CORPORATION OF DELAWARE ms Ann rosy azonynsrurrs N0 Drawing. Application filed May 2 9, 1.?28, Serial No.- 281,586, and in Germany June 10, 1927.

inc present invention relates to new disand pol yazodyestufi's and to a process of pre-' groups being linked to carbon atoms, are

valuable products for dyeing purposes.

These dyestuffs may be prepared by condensing two similar or dissimilar molecules of amino-azo-compounds with such a heterocyclic compound as contains two successively replaceable halogen atoms; or the latter compounds may be condensed with one molecule of an amino-azo-compound and one molecule oi an amino componuds, the radical of which is capable of coupling with diazocompounds after the condensation, and reacting upon these condensation products with diazo-coinpounds. Thereby it is to be understood that the sequence of reacting upon the dihalogenheter'ccyclic compounds with the two com.- ponents may be changed about without departing from our invention. Alsoit is possible to prepare such dyestuffs by reacting upon a heterocyclic compound of the kind above referred to with one molecule of a compound-of the kind 1 r n or the like replacing the second halogen atom by the residue of an amino azo compound and then diazotizing, ii. necessary, after reduction or sapeuification, and coupling with any desired. coupling component. Obviously the preparation of these dyestuil's is not limited to the methods above described but thelatter are only mentioned by Way of example.

Among the heterocyclic compounds containing two successively replaceable halogen atoms the following may, for example, be mentioned 5-chloro-nicotinic acid chloride, trichloropurine, trichloropyrimidine, methyl-dichloropyrimidine, phenyl-dichloro-pyrimidine, dichloro-benzopyridazine, dichloro-aceto-guanamide, 2.l-dichloro-quinazoline, 4-.4-dichloro-G.6-diphenyl-1.l-, 3.3-bis-diazine, Q-phen'yl- 3-carbonic acid chloride) lv-chloroquinazoline, 2A.?" trichloro quinazoline, 2. dichloro-5.7 dibromo quinazoline, lphenyl-(4-carboXylic acid chloride) -4-chloro-phtha-azine, 2-chloro-quinoxaline 3 carboxylic acid chloride, 2.3-dichloro-quinoxaline-(i-carboxylic acid chloride, 2.4l-dichlorocopazo-line, 2.4-diehloro-benzo-10-mona zine-1.3-diazine (cfuBerichte der deutschen Chemischen Gesellschar't, vol. .34, page 1841) and 2%dicholor-l.3-diaZine'- 5;S-diaZine.

The following are examples of compounds which, as described above, may be employed for the introduction of aminoazo residues: the mono acidyl-arylene diamines, phenylene diamine,'the 3- or'l-nitro-aryl amines and the 3. or l-arylene diamine sultonic acids.

The following are examples of amino compounds the radical of which is capable of coupling with a (haze compound after the con densation: Amino hydroxy compounds of the naphthalene series, such as aminonaplr tholsulfonic acids, naphthalenediamines,

such as .1.8-11aphthalenediamined sulfonic acld and substltution products thereof, and

also aminoaryl-pyrazolones with an unoccupied l-p'osition in thepyrazolone ring.

The products thus obtainable may be symmetrical or unsymmetrical ones, but we prefer the latter type, especially those which correspond to the probable general formula NR NHXNHR,- T=NR wherein X represents the residue of a heterocyclic compound, R the residue of a compoundot the'group comprising sulfa and carboxylic acids of the benzene and naph thalene series, the nuclei of which may be further substituted, R the residue oi a compound of the benzene or naphthalene series, R the residue of such a naphthol sulfonic acid compound as couplesin o-position to the OH group, R, the residue of a compound of the benzene series and R the residue of a compound of the group comprising salicylic acid, the nucleus of which may be further substituted, and compounds containing uct obtained in accordance with the applicawherein X stands for the radical of a hetero- T matic residues each containing at least one saponifying the axe dyestuff obtained from low solution, the whole is cooled to 5 C. and coupled with 503 parts by weight of the diazo formation of the dyestufl begins at once accompanied by a deep greenish yellow coloration of the solution and is soon complete. The

new dyestulf dyes cotton green shades of very satisfactory fastness to light.

The dyestuff has in its free form the probable formula:

CH group capable of coupling with diazocompounds, such as pyrazolones with an unoccupied 4-position in the pyrazolo ne ring, the l lI-lgroups being linked to carbon atomsin accordance withthe valuable properties of the dyeings obtainable by means of these dyestuffs.

V v I i V on NI: lo-c 011 007115 l I I iyn N=N -N=N 7 $0311 UH; HO3S a V Hons coon NEN -on When carefully reducing it by means of stannous chloride and hydrochloric acid, it yields among other products a compound of the probable formula: V

All these dyestuffs which correspond to the general formula:

represent dark powders, soluble inwater in form of their alkali metal saltswith bluish green to green: colorations, dyeing cotton clear bluish green to green shades of good fastness especially to light. \Vhen carefully reducing our new dyestuffs with 'stannous chloride and hydrochloric acid theyyield amongother products a compound of the general formula: t

A clear green which is likewise very fast to light is obtained as follows: The condensation product obtained in accordance with the application Ser. No. 240,074 from one molecule of 2.4-dichloro-quinazoline, one molecule of 1-amino-2rhydroxynaphthalene- 3:6-disulfonic acid and one molecule of et-amino-phenyl oxaminic acid is coupled with the monoazo dyestufl from one molecule of 1-amino-8-hydroxynaphthalene-efidisulfonic acid and 3-amino-et-cresol-hydroxy-ethyl ether. The oxalic acid residue is then removed by saponification with excess caustic soda solution. The resulting product is again diazotized (at about 30 C.) and coupled in the presence of sodium carbonate with the acetoacetic acid ortho-chloroanilide mono-sulfonic acid, obtained according to the application Ser. llo. 234,031. A similar dyestull' can also be produced on the fibre by developing with methyl-phenylpyra-z olone, a green shade of very satisfactory fastness to washing and light being obtained.

The process may likewise be carried out by first saponifying the condensation procluct from one molecule of 2.4-dichloro-quinazoline, one molecule 0f'11-amino-8-hydroxynaphthalene-3.6-disulfonic acid and one molecule of 4-amino-phenyl-oxaminic acid, diazotizing the saponification prod ct, then coupling, advantageously in the presence of cyclic compound, R and B represent aroainiuo group.

The following cxan'iples illustrate our invention, without limiting it thereto:

Example J.-A concentratedaqueous solution is produced from 822 parts by weight of the tri-sodium salt of the condensation prodtion Ser. No. 240,074; from one molecule of .2.t-dichloro-quinazoliue, one molecule of 1- amin0-8-hydroXy-naphthaleue-flfi-disulfonic acid and one molecule of t-amino-5-methoxy- 4'hydroXy-azobenzene-3 carboxylic acid. (The latter compound can be produced by diazotized demino-phenyl-oxaminic acid and 3-methoXy-2-hydr0Xybenze-ne 1 carboxylic acid, the so-called guaia-col carboxylic acid). 1100 parts by volume of commercial pyridine are added to the clear reddish yelcompound of theaminoazo body from 1- amino-8hydroxy-naphthalene-3.6-d1sulfon1c acid and 3--am1noAscresolethylether. The

iii/cease i 7 i1aphthalene-3.ti disuliionic acid and one molecule 0t a.annno-phenyl-oxamimc flCltl' with the diazo compoundinom-1-aniino-8- hydroxynaphthaleneeei' disulfonic acld and 3-am1no4;-cresolhydr0xy-ethyl-ether, further diazotizing and coupling in the pres-. ence of sodium carbonate with the acetoacetic acid ortho-chloro=anilide-niono-sultonic acid.

liiloreover. green to 7 olive green tetrakisazo dyestufi s of excellent fastn'ess. to lightare obtained by coupling the condensation product from one molecule of 2.4edichloro-quina- .1 zoline, one molecule of 2-amino-h-hydroxynaphthalene-T-sulfonic acid and one mole cule of an aminoazo compound obtained by saponifying an azo dyestufi from le-aminoacetanilide and a pyrazolone, especially the l-(2-sulfophenyl 8rmethyl-ES-pyrazolone with diazo disazo compounds, such for example i as that from v aniline-2.5-disultonic acid azo-l-amino-naphthalene-7-sultonic acid-azo-1-amind1iaphthalene and the P like.

The 2.-dichloi'mquinazoline used in: the above example can be replaced by similarly constituted halogen derivatives of other heterocyclic. compounds, in which the hetero cyclic ring is. united to a carbocyclic ring, such for example as 1.4-dichloro-phthalazine and the like. Compounds of this kind have been enumerated among others in the body of this. application. i

Emampie .Q.732 parts by'weight of the sodium salt of the condensation product (obtained by successive replacement of the two halogen atoms) from one moleculeoii methyl-dichloro-pyrimidine, one molecule of 4:-

amino f-l hydroxyazobenzene 3" carboxylic acid. and one molecule of l-amino-S-hy- (lrofrynapthalene-3.6-disulfonic acid, are dissolved with the addition oi ezmctly the necessalty quantity of HQUHHIIH ammonia in the smallest possible quantity of hot water. The

above mentioned product is obtained by con-. (lGIlSlllQ; one molecule of methyl-dichloropyrimidine with one molecule of the mono sodium. salt or sl-amino l hydroXy-azobenzene3.-carboxylic acid in aqueous solution at about 50 C. and then decomposing the intermediate compound, which still contains a reactive halogen atom, with one molecule of the acidsodium salt of 1-amino-8-hy-,

droXy-naphthalene-3.6-disulfonic acid in the mentioned su presencclof excess sodium acetate at a raised temperature. The compound has the following properties:

v lti's a greyish yellowpowder. soluble in water; with a purse yellow coloration, when coupled. inpthe presence oi? sodium carbonate hediazotized su'lf'anilic' acid, a red dyestuffis obtained. v

LOGO-parts by volnmeof pyridiiie are now added, the solution is cooled to 5 -C. and,

while-stirring well an icecold paste of the (haze-compound, obtained in the'known manner fromollZ-l partsby weight'of the dyestu'ii' from 1-aminc.--8.naphthol-3.(i-disultonic acid and 3amin0T4:crehol-ethyl-ether -is introduced in a thinstream. Coupling begins at once accompanied by a deep green, coloration of the solution andisisoon complete. The solution. is then diluted with littlewater, the

' new-product is salted. out and Worked up in the 'cust-omary manner. The new dyestuii dyes cotton, forexanipld from, a sodium sul fate-sodium carbonate bath, bluish green shades of very good fastness to light. 7

. Instead of the aminoa zo' compound mentioned; I obtained from l-amino;8hydroxynaphthalene-3J6disulfonic acid; and 3-ami-. no-l-cresol-ether there can housed the aminoazo compound obtained from the sulfuric acid ester of l-amino l-cresobhydroxyethyl-ether (of. U. S. Patent'l,644:,52l or that from 1-amino-8-hydro:i:y-naphthalone- 4.7- (or 6-)-disulfonic acid or also frondlamino 8 hydroxynaphthal ne-5.7-disulfonic acid and 3Tamino-tcresol-methyl-ether or that. from l-aniino-8 hydroiiy naphthalene lv("or 6-);-I;n on o-sulfonic acid-and the above ric acid'ester of 3-amino-4lcresol-hydro-Xy ethylether or also in particular the aminoazo compound from diazoti'zed l-amino -B-hydrox naphthalene-4on1- f0-6-carlooxylijc'- acid and the B-(Q-aminmmethyl-phenoxy)-propi onic acid of the :for-

'. ocnic'n ooon By replacing the aminoazo compounds of the type mentioned by other aminoazo compounds, such, for example, as that from ani- 'lineQ-sulfonic acid (or l-ainino-acet-anilide 3-sulfonic acid) and 1-amino-ilaphthalenc or that "from 2-amino-naphthalone-S-sulfonic acid'or also from 1-amino-8-1nethoxy-naphthaljene-El.6-disulfonic acid and l-aminonaphthalene or other suitable middle components of the benzene or naphthalene series, dyestuffs are obtained likewise dyeing cotton green and possessingvery satisfactory fastness properties.

The shade of the dyestufis of the above example becomes more yellow by using instead ot' the condensation product therein] employed, that, for example, from one molecule of methyl-dichloro-pyrin1idine, one molecule of l-amino-S-hydroXy napl'1tl1alene-Z-3;5-- disulfonic acid and one molecule of l-amino-Q- methoxy methyl 4 hydroxyaz obenzenes 3-carboi ;ylic acid (obtained, for example, by partial reduction of a monoazo dyestuii' derived from 5-nitro-2-amino-anisol-orthocresotinic acid) or of anaminoazo compound oi similar constitution. v Instead of the 'methyl di-chloropyrimidine there can be used with the samesuccess heterocyclic compounds of similar constitution possessing two successively replaceable halogen atoms. The aminoazo compound may then be first condensed, as in the above example, or also, for example,'an amino-hydi'oxyiiaphthalene sulfonic'acidmay first be brought into reaction. A number of such compounds having difierent reactive halogen atoms is mentioned above.

Example 3. 95 parts by-weight ofthe di sodium salt of 4-.-amino 3-methoxy-azobenzene-5-sulfo-3'-carboxylic acid are dissolved in the least possible amountl'oi' Water 198 parts by weight of 2.4-dicl1lo1o quinaZoline are introuuced into this solution at d0 C. with ctlicient stirring, a little acetone is added and the temperature is maintained at SOzH benzenc=2.5-disulfonic acid, l-a-minonaph- -thalene-7-sulfon1o acid and 1-am111onaphly dropped in with very eflicient stirring the solution obtained as described above of the condensation productfrom one molecule of 2.4-d1chlor0-qumazoline and one mole: cule of .4-ammo-3-metl1oxy-azobenzene-5- 'sulfo-3-carboxylic acid, Which still contains a reactive halogen atom. The temperature giust be kept constant between and '85" sluggishly the additiono't a catalyst, say, of potassium bromide, is advantageous. lVhcn all the liquidhas been added heating is continued for another hour at 90C. when the product is salted out and filtered. The new dyestufi' possessing in the-form of the free acid probably the following formula:

is in the pure state a dark powder with a metallic surface lustre. It dyes cotton, for

example, from a sodium sulfate bath, green shadesof very satisfactory fastness to light.-

Dyestulls of the same type can be obtained, forexample, as follows: The condensation product produced in an analogous inanner to thatfused in the above process from one molecule of 2.4-dichloro-quinazoline, one'molecule of the trisazo dyestufi obtained from l-amino-benzene-2.5 disulfonic acid, 1-an1ino-naphthalene-7 -sulfonic acid a second molecule of the same compound and Q-amino-5-hydroxynaphthalene 7 sulfonic 'acid (coupled Whilst alkaline) and one molecule of a-amino-phenyl-oxaminic acid is saponified by means of an excess of sodium hydroxide with heating, The resulting amino compound, of the probable formula:

503K SOaH NHrO-NH M Since the condensation proceeds rather ;is .againdiazotized at ordinary temperature,

sodium carbonate with l -(2--carboXy-,5'-

chloro-phenyl) -3-inethyl-5 pyrazolone. Cotton is dyed a greenshade irom a sodium sulfate bath, possessing very satisfactoryv fastness to light; the dyestuif dyes well on 0. 5 1

Ziamnple .t-illhe diazo componn ta-ined inkthe customary imanner i'rom- 307 parts by weid'htlof the aminoazo compound from 3-amino-iZ-lrydronyTben-soic acid andal auiinonaphthalene is conpledin theprnsencc of sodium carbonate with-732 parts by weight Of: the comlensation pro (ll-1Clhli59d in Example 2 and obtaiuedrfromone ln-olecul proportion of methyl-dichloropy-inmdme, one anolecular proportion oi il-amine S-hydroxynaphthalene-3.6edisulfonic acid and one molecular proportion of 4-amino-4F-hydroxyazobenzene -3 -carboxylic acid. The new yestufi dyes cotton from a sodium sulfate-sodinm-carbonate bath green shades, which :on after-treatment with copper salt ehangetoa deep olive green of eizcellentffistness to washing and light.

By replacing in this example the diagoazo-compound from 3-:ainino+-2+hydr0Xyben- 'zoic .iacidand Lemme-naphthalene by that from -amino-lfi-dimethyl benzene 5-sultonic acid and 1-amino-2 naphthol-ethyle V cther-B-sulfonic acid, a tisazodyestuff is produced which yields on cotton pure green shades of very satisfactory fastness tolight;

Example 5.An aqueous'paste is prepared of 783 parts by weight of the condensation product obtained from .one molecule of dichloro aceto-guan-armide, one moleculeof 1- I amino 8.-hy droxyn aphithaleneediddisnlfonic acid and one molecule of -l-a1i1ino-4 -hyd11o;;yazobenzener3'-carbonylic acid. @nthe addition of 1,060 'parts by volume; ofpyridine, solution takes place with a reddish yellow coloration. The solution is cooled to 0 C. and stirred well during the addition in small portions of an ice cold paste of the diazo compound, prepared in the known manner, from 467 parts by weight" of the dyestuli from 1 amino :8 -.hydroxy -naphthalene-3..6- disulfonic acid and 3-amino-ll cresolsmethylether." The-coupling begins gatwonce accom- ,panied by a ,deep green coloratioinand is soon complete. The working .up. is eflected as; in ExampleQ. Tillie new ,dyestufi dyes cotton, for example, r11101111 a so dinn'i sulfate-sodium caiwbonate bath, in" clear, green shades, .very fast to light; itisalso verv suitable ;for the dyeing of mixed wool andcotton materials.

The; condensation product used in this example as the coupling component is produced by gfirst treating; (at {about 3O" C.) ,1 nolecular quantities of ,dichloroeaceto-guanamide (obtainable, tore-Xample, by means of the chlo- -r-ides. lei phosphonus from I the knownacetowith l-aniino 8=hydroxy-naphthalene- 3.6edisulfonic acid,gthen again treating (at (id- 0.). with a-amino i?-hydroxy-azobenzene-3.- carboxylic acid the intermediatecompound formed, which still containsa reactivegchlorinentom. lllhe 116w co n powder, soluble in water coloration. Coupled with sodinm carbonate solution it'forms ared' dyestuil. I f

By replacing in the above example the diazo component obtained fromcthe azo compound from 1 a-mino-S-hydroxynaphthalone-3.6-di sultonic .acid and 3-amino l-cresol-methylother by that from a-ami no-tolucnc-il-sultonic acid and l-ainino-Q-ethoxy-naphthalene-d sulfonic acid, a dyestufl is produced, dyeing cotton pure fast green shades. By using however, as the dia'zo component the aminoazo compoundfrom 3-amino-2-hydroxy-benh a pure yellow diazo-benzene I in i on red is a yellow I zoic acid and l-amino-naphthalene, .a dyestud is obtained, dyeing cotton from a sodium sulfate-sodium.carbonate bath bluishample, from 2-amino 4-hydroXy-3-carboXydiphenylsulfone-l-sulfonic ,acid, l-aminonaphthalene and the condensation product of dichloro-aceto-guanamide,' 1 amino 8 hydroxy-naphthalene-il.6 disulfonic acid and 4-aminoei-hydroXyaz'obenZene-3-carboxylic acid and then treating the dyeingwith copper salts. 1 Q V Emmnple 6'.-The diazo compound obtained from 107 parts by weight or": 41aminc-toluene is coupled at 0 C. advanta ngcously w" h the addition of alittle pyridine. with a sodium carbonate solution of parts by weight of the condensation prodnct desmfibcd in EX ample l. and obtained 1" rom' one molecule of la-diclilo-ioquinazoline, one molecule of 1- amino l-hydroxynaphthalene-3.6-disulfonic acid and one molecule of l-amino-5-1nethyl- 4-hydroXy-azobenzene3 carboxylic' acid. The dyestuil after working up in the customfactory fastness to light.

. trisazo dyestuff obtained, as in the above eX- E sample 1') .The diazodisazo compound produced in the known manner from 685 parts by weight of the disazo dyestuf't from anilineQ-sulionic acid; 1-aminonaphthalene- 7- sulfonic acid and 1-amino-Q-ethoxymaphthalene-G-sulfonic acid is coupled at 5 C. in the presence of much pyridine with 4:64 parts by weight of the reduced condensation product from one molecule of 5-chlo'ro-nicotinic acid chloride, one molecule of Q-amino- 5-hydroxynaphthalene-7-sulionic acid and one molecule of 3-n-itro-1:methyl aminobendissolving once (advantageously in the'pres ence of a little ammonia) 'itdyes cotton blue shades b diazotization and develooment with methyl-phenyl pyrazolone green shades are produced fast to washing, light and top- I ping.

The reduced condensation product of the probable formula:

used in this example as coupling component,

' is produced by condensing at a low'temperature molecular quantities of 5-chloro-nicotinic acid chloride and 2-amino-5-hydro:;ynaphthalene-7-sulfonic I acid, then replacing the halogen atom in thenucleus by 3-nitro-1- methyl-aminobenzene under pressure in a stirring autoclave in thep 'esence of sodium acetate and advantageously ofa little dioxane and then reducing the nitro groupffor instance, with iron and acetic acid.

The condensation product used in the above example may be replaced by that from one molecule of dichloro-acetoguanamide, one molecule of 1-amino-8-hydroxynaphthalene- 3.6-disulfonic acid and one molecule of 3-mtro-aniline with subsequent reduction for example, by iron and acetic acid; the resulting compound is a grey powder, soluble in ,water with a yellowish coloration, it can be diazotized and the diazo compound gives on pouring into sodium carbonate a red 'dyestufil On coupling this compound with the amino-- azo compound from i .fi-(liClllOlO-filllllhQ-Q sultonic acid and LaminO-Q-ethOXynaphthalene-6-sulfonic acid after diazotizing in the known manner a disazo dyest-ufii is produced, dyeing cotton a pure blue: diazotized on the fibre and developed with methyl-phenyl pyrazolone a pure green fast to washing and light results.

Example 8.1 99 parts by weight of L6- dinitro-2-amino-1-hydroXy-benzene are diazotised and coupled at +5? G. with asodium carbonate solution of 601 parts by weight of the condensation product from one molecule of dicholoro-aceto-guanamide, one molecule of 2-amino5-hydroXy-naphthalene-7-sultonic acid and one molecule of d-amino5- methyl 4-hydroxy-aZobenzene-3-carboxylic acid the preparation is analogous to that of the coupling component used in Example The coupling is soon complete; The dyestuit after working up in the customary manner dyes cotton yellowish brown shades. which change on after-treatment with copper salts into a brown of Very satisfactory fastness to light and washing. A yellow of the same properties is obtained by coupling the dye molecule st-ufffr'om the condensation product'fof one molecule of dicholoro-aceto-guanamide, one

azoberizene-EBcarboxylic acid and one mole- 3-amino-2- hydroXy-benzoic acid in sodium carbonate solution.-

Weclaim: 1 i 1. Process, which comprises reacting upon such a heterocyclicr compound as contains two successively replaceablehalogen atoms with one molecule of an amino-aZo-compound and one molecule of an amino coinpound,the radical of which is capable of coupling with diazo compounds after the condensat1on,and reacting upon these condensation products with a diazo compound.

2. Process, which comprises reacting upon couples in o-position to the OI-I-group and couplingthese condensation products with a diazotized amino-azo-compound.

3. Process, which comprises reacting upon such a'heterocyclic compound as contains two successively replaceable halogen atoms with onemolecule of a compound of the probable formula:

coon

wherein the benzene nuclei may be otherwise substituted and one molecule of such a periaminonaphthol-sulfonic acid as couples in o-position to the CPI-group, and reacting upon these condensationproducts with a diazotized compound of the probable'tormula:

a compound'of the group comprisingsuch .diazines and triazines as contain two successively replaceable halogen atoms with one molecule of an amino-azo-compound and one molecule of an amino compound, the radical of which isca pable of coupling with diazo compounds after the'condensation, and reacting pon these condensationproducts with a diazo compound. 7

5. Process, which comprises reacting upon a compound of the group comprising such diazines and-triazines as contain two successively replaceable halogen atoms with one ,molecule or an aminoazo-compound of the ben'z-enejseiics containii'ig sulfo- 'orcarbo'xylic acid groups, a and onemOlecule of such an aminonaphthol sulfonic acid compound as couples in o-posinen to'the OH-group and coupling these "condensation products Witha 'd'i'az'otilzed"amin'o azocompound; Y

6. Process, which comprises reacting upon a compound of the group comprising such diazines as contain the heterocyclic ring 'system condensed with a benzene mug; and

which contain two successively replaceable halogen atoms, with one molecule of a compound of the probable formula:

(DOOR wherein the benzene nuclei may be otherwise substituted and one molecule of such a periaminonaphthol-sultonic acid as couples in o-position to the OH-group, and reacting upon'these condensationproducts With ajdia zotized compound of theprobable formula:

SOiH

Whereinthe and nuclei may be otherwise substituted.

7. Process, which comp QA-dichlOroquinazoline of the probable formula:

\N//(' Cl with one molecule of the compound of the probable formula:

com

coon and one molecule of l-am'ino-8-hydroxynnaphthalene-3.ti-disulfonic'acid and coupling 1 this condensation product with one molecule of a diazotized compound of the probabie formula O.C2Ha

formula 'ises reacting upen 8. Azodyestulis' of the probable general wherein X represents the residue of a heterocychc compound, R and R5 stand for the residues of anjiles'iredazo compounds, the p to carbon atoms,

NH-groups being linkec said product's beingstrongly colored powders, yielding on careful reduction Wi'th'stain nous chloride, and hydrochloric acid among other products for nulai ni-mn xennnn V 'wherein X represents the residue of a heterocyclic compound, R and P stand for the residues of aroi'natic compounds,, each containing at least one amino, group, the NH-groups being linked to carbon atoms.

a compoundof the general 9. Azod estuiis of the .robable ecneral y a p P v i e of sa-licyclic acid, the nucleus of which may 7 be further substituted andcompounds con taining a -CH group capable of coupling with diazocompounds, the '-NH groups being linked carbon atoms; said dyestuffs being dark powders, soluble in water in form of their alkali metalsalts with bluisl1- to green to olive-green coloi'a'tioiis, yieh n on carefulreductien with stannous chloride and hydrochloric acid amouiit other products a compound of the probable general formula:

. wherein X represents the residue of a heterocyclic compound, R means the residue of an aminonaphtholsultonic acid compound and R the residue of a con'ipou'nd of thebenbzene series containing an amino grou the -NH'- groups being linked to carbon-atoms.

10. Azody'estullfs having in'theirfr'ee for'in the probable general formula:

Son JV careful reduction withstannous chloride and hydrochloric acid among other produces a coiu mundof the probable formula:

. w NHJNHONHQ wherein X stands for the residue of a heterocylic compound and wherein the aromatic nuclei may be further substituted, the H groups being linked to carbon atoms. 11. Azodyestuiis of the probable general formula:

wherein X rep sents the residue'of com-' pound of the. group consisting of diazines and triazines, R and 3 stand for the residues of any desired azo compounds, the TH groups being linked to'carbon atoms, said products being strongly colored powders, yielding on careful reduction with stannous chloride and hydrochloric acid among other products a compound of the general formula wherein X represents the residue of a compound of the group consisting. of diazines and triazines, R and it; stand for the resi- I dues of an aromatic compound, each containing at least one amino-group, the -N Ed groups being linked to carbon atoms.

12. Azodyestufis of the probable general formula:

wherein X represents the residue of a compound of the group consisting of diazines andt iazines, R the residue of a compound of the group consisting of sulfoand carboxylic acids of the benzene and naphthalene series, the nuclei of which may be further substituted, R the residue of a compound of the benzene or naphthalene series, R the residue of such a naphthol sulfonic acid compound ascouples in o-position to the OH- group, R the residue of a compound of'the benzene series and R the residue of a com pound of the group consisting of salicylic acid, the nucleus of which may be further substituted and compounds containing a groups being linked to carbon- CH group capable of coupling with diazo compounds, the ;NH- groups being linked to carbon atoms; said dyestuffs being dark powders, soluble in water in. form of their alkali metal saltswith bluish-green togreen colorations, yielding on careful reduction with stannous chloride and hydrochloric acid among other products; a compound of theprobable general formula V .R N H=XNHR wherein X represents the residue of a. compound of the group cons sting of diazines and triazines, H means the IGSKl LKXOf an aminonaphthol-sulfonici acid compound and R the residue of a compound of the benzene series containing an, amino group; the

NH rou bein linked to carbon atoms.

r 13. Azooyestufls having 111 their free form the probable general formula:

.-o-n i. I

sognj wherein X represents the residue of such a diazine contains the heterocyclic ring systern condonsedwith a benzene ring, R stands for the residue of a compound of the group consisting of salicyclic acid and compounds containing a OH group capableof coualmgwith diazocompounds and wherein the aromatic nuclei may be further substituted, the NH' groups being linked to carbon atoms said products being dark powders, soluble in water in form of their alkali metal salts with green colorations, yielding on' careful reduction with stannous chloride and hydrochloric acid among other products a compound of the probable formula:

SOaH wherein X represents the residue of such a diazine as con'tains'the heterocyclic ring system condensed W1 th a benzene ring and wherein'the aromatic nuclei may be further substituted.

141 The azodyestuifs having in its free form the probablegeneral formula:

OCH3

said dyestufl being adark powder, dyeing cotton yellow green shades of very satisfactory properties to light, yielding on careful,

reduction With stannous chloride and hydrochloric acid among other roducts the compound having in its free orm the probable ormula aN I NH NH2 1103 S S 0:11

In testimony whereof we have hereunto set 

